CN109179460A - A kind of production method improveing magnesium sulfate monohydrate - Google Patents
A kind of production method improveing magnesium sulfate monohydrate Download PDFInfo
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- CN109179460A CN109179460A CN201811036568.3A CN201811036568A CN109179460A CN 109179460 A CN109179460 A CN 109179460A CN 201811036568 A CN201811036568 A CN 201811036568A CN 109179460 A CN109179460 A CN 109179460A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/08—Preparation by working up natural or industrial salt mixtures or siliceous minerals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The present invention relates to a kind of production methods for improveing magnesium sulfate monohydrate, obtain at 50 DEG C -80 DEG C and mention magnesium raw material liquid containing chlorine is highly concentrated, and Cl-:SO42- molar ratio should be met less than 6 by mentioning magnesium raw material liquid, and Mg2+: Na+ molar concentration rate is greater than 2.1.Magnesium raw material liquid will be mentioned to import in container for evaporation, it is mixed with the mother liquor in container, Cl-:SO42- molar ratio is greater than 6.5 in mother liquor, SO42-: Na+ molar ratio is greater than 0.25, and Mg2+: Na+ molar concentration rate is greater than 2.2, carry out 80 DEG C or more of high temperature evaporation, evaporation terminal is determined according to evaporating pressure and boiling temperature, Con trolling index is upgraded to boiling point, boiling point rises 13 DEG C~18 DEG C of range, complete evaporation of liquid is separated by solid-liquid separation in 70 DEG C or more completions, it obtains magnesium sulfate monohydrate and crystallizes wet solid phase, magnesium sulfate monohydrate is cleaned in such a way that mother solution displacement or alcohol are washed crystallizes wet solid phase, go dechlorination component, obtain sulfuric acid monohydrate magnesium crystal.The resulting magnesium sulfate monohydrate average particle size of this method is greater than 160 microns, is easy to be separated by solid-liquid separation, product purity height, good fluidity.
Description
Technical field
This patent belongs to the salt separation and field of comprehensive utilization of Brine resources, brine waste, mixed salt material, is related to producing
Low chlorine sulfuric acid monohydrate magnesium products are the method for a kind of production of high-sulfur brine sodium chloride and magnesium sulfate monohydrate with high salt by it.
Background technique
One, the production method about sodium chloride and magnesium sulfate in the comprehensive utilization of Brine resources
Beach is widely used at present and shines evaporation salt manufacturing or beach solarization saturated bittern vacuum salt two ways for preparing salt by working up seawater.
The salt-making mother liquor of two kinds of salt manufacturing modes, perhaps discharge or using conventional method comprehensively utilized.By the way of discharge
It is that environment is disagreeableness.Traditional comprehensive utilization mode be using producing potassium chloride by halogen conversion method as core, major product have potassium chloride,
Magnesium chloride (halogen piece, halogen powder), sodium sulphate, bromine etc..Salt-making mother liquor is blended into be made with the magnesium chloride bromine mother liquor as main component that mentions
The concentration proportion of magnesium sulfate and magnesium chloride reduces in brine, while the ratio of magnesium chloride and potassium chloride improves, the mixing after converting halogen
Halogen is evaporated at 100 DEG C or more, and sodium chloride and magnesium sulfate is precipitated sufficiently, and warm sedimentation separation goes out with sodium chloride and sulfuric acid monohydrate
Magnesium salt-mixture as main component, is commonly called as high and tow temperature salt.Clarified solution, which further cools down, is precipitated carnallite, and carnallite decomposes production again
Potassium chloride.Carnallite mother solution then further mentions bromine and production magnesium chloride.
High and tow temperature salt starts to be only used as abraum salt, carries out separation production magnesium sulfate monohydrate to it later.Separation method is in 60-70
Age invades method using dissolution freezing or thermosol.The 80-90 age is being tied using magnesium sulfate monohydrate in high and tow temperature salt and sodium chloride
Significant difference in grain size, using physical method, such as concussion method, press over system, cyclone method, the mixing that high temperature evaporation is precipitated
Salt is separated into magnesium sulfate monohydrate slurry (magnesia magma) and sodium chloride slurry, and obtained magnesium sulfate and sodium chloride quality are low, magnesium sulfate
In contain a large amount of sodium chloride.Ox contented (1994) develops the production work with cyclone and sedimentation-type centrifuge separating high-temp salt
Skill.Salt slurry magnesia magma obtained after separation is mixed, based on magnesium sulfate, but containing fine salt and evaporation mother liquor, it is directly filtered, then
The mother liquor in magnesia magma is pushed away with water, but keeps magnesium sulfate loss very big since magnesium sulfate is easy dissolution.
The mass concentration of evaporation of seawater to magnesium is greater than 4% with solarization method by Glassett (1970), and brine volume is added
10% clear water, -5 DEG C are cooled to, to produce magnesium sulfate.
Fernandez-Lozano (1974) to specific gravity be 1.30g/l solarization bittern, be added volume ratio be 5% it is clear
Water is cooled to -5 DEG C, recycles in bittern 70% magnesium sulfate.Magnesium sulfate is washed with cold water, and 70 DEG C of dryings, epsom salt contains
Amount is 96%.
Arakel (1993) is different from the method for Fernandez-Lozano, bitter to the solarization that specific gravity is 1.28-1.30g/l
Halogen is cooled to 0 DEG C to -5 DEG C and obtains crude magnesium sulfate, all with hot water dissolving and to be evaporated to specific gravity be that 1.28-1.30g/l exists again
20-25 DEG C of crystallization.
The patent DE10256046 of BACH JUERGEN (2004) produces sodium chloride and epsom salt using bittern.It adopts
With two set of two effect vaporising device.Addition circulating mother liquor makes the ratio of magnesium sulfate and magnesium chloride be increased to 0.25~0.5, uses first set
Device is concentrated by evaporation to magnesium sulfate and is saturated, and the sodium chloride of evaporative crystallization is separated, as refined salt product.Complete evaporation of liquid adds water cooling to freeze
Crystallize epsom salt.Freezing mother liquor continues with second set of vaporising device, carries out dual circulation, and removal impurity salt keeps mother liquor net
Change, purified mother liquor, which walks around to convert, adjusts magnesium sulfate and magnesium chloride ratio, the ratio about 1:1 of mother liquor amount and material quantity in raw material.
In this invention, need to be equipped with a set of dual circulation crystallizer dedicated for going out low-quality carnallite.
Applicant Zhou Huan reports the method (Chinese patent that sodium chloride and epsom salt are produced with brine early period
CN200810054198.6): step: (1) brine is raw material, and SO42-: Mg2+ molar ratio is 0.1~0.8 in brine, and
SO42-: Na+ molar ratio is 0.025~1；Decompression boiling evaporation, control pressure when bringing the evaporation to completion boiling temperature be 75 DEG C~
50 DEG C, and SO42: Na+ molar ratio is 0.4~2.5 in solution；(2) it is separated by solid-liquid separation, solid phase is washed with saturated sodium-chloride water solution
It washs, through being dried to obtain sodium chloride；(3) add water to salt-making mother liquor, mixed liquor is made；(4) mixed liquor is cooling, is introduced into crystallizer
In, there is crystallization to be precipitated；(5) it is separated by solid-liquid separation, obtaining solid phase is epsom salt crude product.Method equipment of the invention is simple, technique
Simply, abundant, the purity and high income of epsom salt that sodium chloride is precipitated realize sodium chloride in the process without carnallite link is removed
With the Joint Production of epsom salt.
In the method that above-mentioned brine comprehensively utilizes production sodium chloride and magnesium sulfate, available sodium chloride and seven water sulfuric acid
Magnesium, or the mixture of magnesium sulfate monohydrate and sodium chloride is obtained, then carry out physical separation.It cannot obtain the low water sulphur of chlorinity
Sour magnesium.
Two, about the production method of magnesium sulfate monohydrate
Magnesium sulfate monohydrate (MgSO4H2O) is a kind of white powdery solids, and sulphur, content of magnesium are high, is widely used in compound fertilizer
Desiccant, agricultural fertilizer and feed addictive etc. are the important basic chemical raw materials of industrial and agricultural production.
Currently, there are mainly three types of the production methods of magnesium sulfate monohydrate:
1, sulfuric acid process
Chinese patent (1109845 A of CN) reports a kind of concentrated sulfuric acid and the (oxidation in such as calcined magnesite containing magnesium slag
Magnesium carbonate etc. in magnesium, raw magnesite) it is directly mixed to prepare magnesium sulfate monohydrate, sulfuric acid monohydrate magnesium products made from this method are pure
It spends low, is simply possible to use in agricultural fertilizer, and the method production equipment seriously corroded, product are rendered obvious by acidity, waste liquid environmental pollution
Greatly.
2, epsom salt evaporation
(1) 2011 year Wang Xin Hong is reported in " inorganic chemicals industry " (2011,43:45-47), directly dry by tray drier
The method that dry epsom salt produces magnesium sulfate monohydrate.Chinese patent (103387248 A of CN 102583459 A, CN) passes through
Epsom salt is dehydrated by Rotatingandflashstreamingdrier or fluidized bed is made magnesium sulfate monohydrate.This method is affected by raw material, and
Energy consumption is higher, and product carnallite content is high, of poor quality.
(2) patent of invention CN201310320368.1 discloses a kind of for preparing the side of magnesium sulfate monohydrate from epsom salt
Method, which is characterized in that the described method includes: epsom salt material is made successively to pass through bed body temperature gradually rises at least two
Fluidized bed obtains magnesium sulfate monohydrate to be dehydrated step by step, wherein range of the bed body temperature of the fluidized bed at 50-200 DEG C.This
Invention utilizes more furnace chamber fluidized bed drying epsom salts, by substep dehydration, prepares magnesium sulfate monohydrate, easily controllable dry
Dry temperature, dehydrating effect is good, and process flow is simple, energy conservation and environmental protection, and economic benefit is excellent.
(3) patent of invention CN201210040066.4 discloses a kind of work of preparing magnesium sulfate monohydrate by using water-containing magnesium sulfate heptahydrate
Skill comprising following steps: the charging of (i) wet stock: aqueous epsom salt is sent into the hothouse of Rotatingandflashstreamingdrier；
(ii) hot wind conveys: air being heated to 220-320 DEG C, and is pressurizeed and is sent into Rotatingandflashstreamingdrier with blower；(iii) it does
Dry process: wet stock to be dried stops 2-6 seconds in the hothouse of Rotatingandflashstreamingdrier, obtain containing free water≤
The finished product magnesium sulfate monohydrate of 3wt%；(iv) discharging and vent gas treatment, discharge: being sent into discharging device by air-flow by dry material,
Through cyclone dust removal, water film dedusting, collect by dry magnesium sulfate monohydrate, exhaust emissions.The aqueous epsom salt system of the present invention
The technique for taking magnesium sulfate monohydrate, drying temperature are easy to control, and process flow is brief, adaptable, drying process is continuous, stablize,
Reliably, drying effect is good.
3, solution-evaporation
(1) patent of invention CN02155485.4 reports a kind of production method of magnesium sulfate monohydrate, will contain 15-35wt%
Adlerika is evaporated to 45-65 ° of Be ' in 30-180 DEG C, separates at 70-150 DEG C, and obtained sulfuric acid monohydrate is then dried
Magnesium.Few with impurity content, product purity is high, and low energy consumption, the low advantage of production cost.
(2) patent of invention CN200810031775.X is reported, a kind of salt-mixture using sodium chloride and epsomite takes a water
The method of magnesium sulfate.It is the following steps are included: (i) mix the salt-mixture of raw material sodium chloride and epsomite；(ii) ingredient, by mixed
Salt 545-555 parts by weight, water 246-256 parts by weight are closed, brine 535-545 parts by weight are prepared；(iii) by the mixture object of preparation
Material is heated to 74 DEG C -76 DEG C, promotes salt-mixture dissolution；(iv) undissolved NaCl is filtered out；(v) undissolved NaCl will be filtered off
Mother liquor afterwards is heated to 74 DEG C -76 DEG C, is concentrated by evaporation, until crystallizing out particulate magnesium sulfate monohydrate and coarse grain sodium chloride；(vi) mistake
Filter, obtains particulate magnesium sulfate monohydrate and coarse grain sodium chloride mixture；(vii) it is carried out at 74 DEG C -76 DEG C using 325 the polished standard screens
Screening, oversize are sodium chloride, and screenings is through 74 DEG C of -76 DEG C of drying to get sulfuric acid monohydrate magnesium products.Operation of the present invention condition temperature
With low energy consumption, and production cost is low, no discharging of waste liquid, no pollution to the environment.
In the production method of above-mentioned magnesium sulfate monohydrate, sulfuric acid process or epsom salt dehydration produce magnesium sulfate monohydrate and this
It invents unrelated.And solution-evaporation, the raw material that CN02155485.4 is used is Adlerika, and CN200810031775.X,
Using mixed salt, what is be evaporated is still mixed salt, needs to be separated using particle size differences, cannot obtain pure water sulphur
Sour magnesium and sodium chloride product.
Summary of the invention
It is an object of the invention in place of overcome the deficiencies in the prior art, provide a kind of high-sulfur brine with high salt to pass through evaporation knot
The method that brilliant technique directly produces sodium chloride and the crystalline magnesium sulfate monohydrate of low chlorine.
The technical issues of solution includes:
(1) high solutions of chlorine evaporation prepares the method and condition of crystalline magnesium sulfate monohydrate.
(2) method of magnesium sulfate monohydrate purification dechlorination.
(3) high-sulfur bittern evaporation salt manufacturing with high salt, and prepare the method and condition for mentioning magnesium solution.
The technical proposal for solving the technical problem of the invention is:
1, the technical solution of crystalloid magnesium sulfate monohydrate is obtained in homadamon border
A. allotment mentions magnesium raw material liquid, obtains at 50 DEG C -80 DEG C and mentions magnesium raw material liquid containing chlorine is highly concentrated, mentioning magnesium raw material liquid should meet
Cl-:SO42- molar ratio is less than 6, and Mg2+: Na+ molar concentration rate is greater than 2；
B. magnesium raw material liquid will be mentioned to import in container for evaporation, mixed with the mother liquor in container, Cl-:SO42- molar ratio in mother liquor
It is greater than 0.25 greater than 6, SO42-: Na+ molar ratio, and Mg2+: Na+ molar concentration rate is greater than 2, in homadamon border, carries out 80 DEG C
Above high temperature evaporation evaporates terminal, is determined according to evaporating pressure and boiling temperature, Con trolling index can be upgraded to boiling point, boils
Point rises 13 DEG C to 18 DEG C of optimum range.Such as: being 65 DEG C in the boiling point that absolute pressure 25kPa corresponds to water, terminal preference temperature should be 78 DEG C
To 83 DEG C；It evaporates, 113 DEG C to 118 DEG C of terminal preference temperature, is evaporated in absolute pressure 200kPa, boiling temperature is no more than under normal pressure
133 DEG C to 138 DEG C.
C. complete evaporation of liquid is separated by solid-liquid separation in 70 DEG C or more completions, is obtained magnesium sulfate monohydrate and is crystallized wet solid phase, impurity is main
For mother liquor entrainment.
2, the purification dechlorination method of magnesium sulfate monohydrate
Homadamon border, high temperature evaporation crystallization to magnesium sulfate monohydrate crystal, after separation of solid and liquid can entrainment mother liquor, cause containing chlorine
It is higher.The method for removing mother liquor and dechlorination is embodied as follows:
A. the wet solid phase for having mother liquor, removes the chlorine component of mother liquor entrainment using the mode that mother solution displacement or alcohol are washed.
B. mother solution displacement refers to, when being separated by solid-liquid separation, sprinkling displacement solvent, continues to filter on solid phase filter cake；Alcohol
It washes, is that wet solid phase is sized mixing with alcohol, agitator treating.
C. the slurry that alcohol is washed obtains the wet solid phase of magnesium sulfate monohydrate, obtains low chlorine sulfuric acid monohydrate through dry by being separated by solid-liquid separation
Magnesium products, chlorine component is usually below 1%.
D. mother solution displacement or alcohol are washed, and used alcohol is ethyl alcohol or methanol；
E. cleaning solution distills bottom liquid, returns to evaporation salt manufacturing workshop section by being distilled to recover methanol or ethyl alcohol.
3, high-sulfur brine with high salt elder generation vacuum salt produces the scheme of magnesium sulfate monohydrate by salt-making mother liquor again
Raw brine includes salt-making mother liquor or comprising main component Na+, Mg2+, Cl-, the brine of SO42-, H2O, especially
SO42-: Cl- molar ratio is greater than 0.08 high-sulfur brine.
A. the molar ratio that raw brine composition meets SO42-: Mg2+ is less than 0.8, and SO42-: Cl- molar ratio is less than
0.25, salt manufacturing can be directly evaporated, and generate high magnesium solution.
B. the molar ratio that raw brine composition meets SO42-: Mg2+ is greater than 0.8 but when less than 1, then needs to mention mother liquid of magnesium and do
Circulation fluid.
C. it when the molar ratio that raw brine composition meets SO42-: Mg2+ is greater than 1, then needs to remove part of sulfuric acid sodium or adds
The brine for entering other magnesium chlorides containing high concentration makes raw material composition meet (a) or requirement (b).
Salt manufacturing is evaporated, using negative pressure single-action or the continuous forced evaporation crystallization process of multiple-effect, the salt manufacturing of multiple-effect evaporation is former
Feed liquid enters system in higher boiling crystallizing evaporator, and mother liquor uses smooth discharge, in the crystallizing evaporator row that boiling temperature is minimum
System out.The solidliquid mixture of each effect discharge by separation of solid and liquid, saturated sodium-chloride salt water washing, is dried to obtain sodium chloride production
Product；
Salt-making mother liquor such as uses multiple-effect evaporation, and mother liquor is discharged using fair current, and system is discharged in the evaporator minimum from evaporation boiling point
Salt system.Salt-making mother liquor can be used as when meeting following condition mentions magnesium brine: the boiling point of row's mother liquid evaporation device is 50 DEG C~75 DEG C,
SO42-: Na+ molar ratio is greater than 1.0, and Mg2+: Na+ molar concentration rate is greater than 2.The acquisition for mentioning magnesium brine is separated using heat preservation,
Or the in line acquisition of overflow in evaporated crystallization device.
Magnesium raw material liquid will be mentioned to import in container for evaporation, mixed with the mother liquor in container, Cl-:SO42- molar ratio is big in mother liquor
In 6, SO42-: Na+ molar ratio be greater than 0.25, and Mg2+: Na+ molar concentration rate be greater than 2, in homadamon border, carry out 80 DEG C with
On high temperature evaporation, evaporate terminal, determined according to evaporating pressure and boiling temperature, Con trolling index, boiling point can be upgraded to boiling point
Should not be higher than by rising by 18 DEG C.Such as: being 65 DEG C in the boiling point that absolute pressure 25kPa corresponds to water, outlet temperature is not to be exceeded 83 DEG C；Under normal pressure
Evaporation, outlet temperature are not to be exceeded 118 DEG C, evaporate in absolute pressure 200kPa, boiling temperature is no more than 138 DEG C.Complete evaporation of liquid exists
70 DEG C or more completions are separated by solid-liquid separation, and are obtained magnesium sulfate monohydrate and are crystallized wet solid phase, the wet solid phase with mother liquor, using mother solution displacement,
Or the mode that alcohol is washed removes the chlorine component that mother liquor is carried secretly.
The advantages of the present invention:
(1) present invention controls boiling point and rises range, obtain crystalline magnesium sulfate monohydrate in the environment of high chlorine by high temperature evaporation,
Resulting magnesium sulfate monohydrate average particle size is greater than 160 microns, is easy to separation of solid and liquid and purifying products.
(2) present invention reaches dechlorination effect using the method that solvent displacement or alcohol are washed, the sulfuric acid monohydrate washed and dried through alcohol
Magnesium does not agglomerate, and has good mobility.
(3) present invention can utilize high-sulfur brine of SO42-: the Cl- molar ratio greater than 0.08 to carry out negtive pressure forced evaporation system
Salt, and magnesium sulfate monohydrate is produced by salt-making mother liquor, comprehensively utilize brine.
Detailed description of the invention
Fig. 1 is the main streams figure that high-magnesium brine with high salt produces sodium chloride and magnesium sulfate monohydrate
1 Dao n effect crystallizing evaporator of A1-An multiple-effect evaporation；B1 mentions magnesium crystallizing evaporator；B2 magnesium sulfate monohydrate solid-liquid point
From；The wet solid phase mother solution displacement of B3 magnesium sulfate monohydrate；B4: magnesium sulfate monohydrate is dry；B5 solvent recovery；The solid-liquid of C sodium chloride salt slurry
Separation, washing drying.
A- feed stream；B- salt-making mother liquor；C- sodium chloride salt slurry；D- mentions magnesium brine；E- mentions mother liquid of magnesium；Mono- water magnesium salts of f-
Slurry；The mono- wet solid phase of water magnesium of g-；The mono- wet solid phase of water magnesium of h-
Fig. 2 is the electromicroscopic photograph (500 times of amplification) of magnesium sulfate monohydrate obtained by the method for the present invention
Fig. 3 is the electromicroscopic photograph (9000 times of amplification) of magnesium sulfate monohydrate obtained by the method for the present invention
Specific embodiment
The invention will be further described with reference to the accompanying drawing and by specific embodiment, and following embodiment is descriptive
, it is not restrictive, this does not limit the scope of protection of the present invention.
Brine according to the present invention is related to seawater, bittern, salt lake bittern, salt lake bittern etc..Brine waste, mixed salt
Material is the salt-containing liquid containing three kinds of substances in four sodium chloride, sodium sulphate, magnesium sulfate, magnesium chloride salt or mixed salt etc., unlimited
It is fixed whether to contain other components, such as potassium ion, bromide ion, borate other components.High-sulfur brine with high salt, refers to sodium chloride and sulphur
The very high above-mentioned brine of the content of acid group or material.Because high-sulfur material with high salt can match corresponding brine, therefore, in specification referred to as
For high-sulfur brine with high salt.
High-sulfur brine of SO42-: the Cl- molar ratio greater than 0.08 is utilized to be evaporated salt manufacturing.
For with Na+, Mg2+, Cl-, SO42-, H2O brine as main component, if SO42-: Cl- molar ratio is greater than
When 0.08, the crystal region of astrakanite or sodium sulphate is in room temperature (such as 25 DEG C)；Astrakanite, nothing are at 50-100 DEG C
The crystal region of water loeweite cannot obtain the production of pure sodium chloride.
This patent defines that evaporation salt manufacturing condition (1) raw brine composition meets, SO42-: Mg2+ molar ratio be less than
0.8, and SO42-: Cl- molar ratio is less than 0.25；(2) vacuum forced evaporation crystallization process is used.Thus it can get high yield
Salt-making process.
Case one (75 DEG C of isothermal forced evaporation salt manufacturing): taking 2000 grams of brine, and group becomes Na+:4.03%, Mg2+:
3.33%, Cl-:11.95%, SO42-:5.40%, H2O:75.29%；Wherein SO42-: Mg2+ molar ratio is 0.41；
SO42-: Cl- molar ratio is 0.17, meets the salt manufacturing range of this patent restriction.75 DEG C of isothermals are carried out in evaporative crystallization to force to steam
Hair evaporates 950 grams of water, carries out isothermal and mother liquor composition Na+:1.86%, Mg2+:7.70%, Cl-:15.64% is obtained by filtration,
SO42-:13.11%, H2O:61.69%.Solid phase washs drying through saturated brine, and obtaining sodium chloride quality is 162 grams, and purity is
99.2%, the eduction rate of sodium chloride is 79.13%.
Case two (100 millibars of absolute pressures, isobaric forced evaporation salt manufacturing): taking 2000 grams of brine, and group becomes Na+:4.03%,
Mg2+:3.33%, Cl-:11.95%, SO42-:5.40%, H2O:75.29%；Wherein SO42-: Mg2+ molar ratio is
0.41；SO42-: Cl- molar ratio is 0.17, meets the salt manufacturing range of this patent restriction.100 millibars etc. are carried out in evaporative crystallization
Temperature evaporation, evaporates 61 DEG C of outlet temperature, evaporates 960 grams of water, and solidliquid mixture carries out isothermal and mother liquor composition Na+ is obtained by filtration:
1.68%, Mg2+:7.88%, Cl-:15.56%, SO42-:13.58%, H2O:61.30%.Solid phase is washed dry through saturated brine
Dry, obtaining sodium chloride quality is 167 grams, purity 99.5%, and the eduction rate of sodium chloride is 81.5%.
Case three (60 DEG C of isothermal forced evaporation salt manufacturing): taking 2000ml brine, and composition concentration is MgCl2:120.0g/l,
MgSO4:118.0g/l, NaCl:140g/l, H2O:818.0g/l, wherein molar ratio=0.44, SO42- of SO42-:Mg2+:
Cl- molar ratio is 0.2, and the electricity consumption heating mantle heats in three-necked flask, three-necked flask connects vacuum pump, makes to expect by controlling pressure
Liquid evaporates 437.2g water, is separated by solid-liquid separation in 60 DEG C of explosive evaporations, and solid phase is washed with saturated sodium-chloride water solution, dry
After obtain 110g sodium chloride, purity is 99.5%；
Case four (raw material tune converts rear forced evaporation salt manufacturing): taking 1041 grams of brine, and group becomes Na+:6.33%, Mg2+:
2.23%, Cl-:8.87%, SO42-:10.03%, H2O:72.54%；Wherein SO42-: Mg2+ molar ratio is 1.14；
SO42-: Cl- molar ratio is 0.41；Two indexs exceed the salt manufacturing condition of this patent restriction.It is blended into brine and mentions mother liquid of magnesium
938 and 22 grams of water, the salt of precipitation is dissolved, Na+:4.05%, Mg2+:4.33%, Cl-:13.75%, SO42- are formed:
6.97%, H2O:70.90%.Wherein SO42-: Mg2+ molar ratio becomes 0.407；SO42-: Cl- molar ratio becomes 0.187.
0.1atm equipressure forced evaporation, 380 grams of water obtain 187.4 grams of sodium chloride, and not washed, entrainment mother liquor amount is 9%, washed
Purity reaches 99.3%.
Therefore, using the method for this patent and restrictive condition, high-sulfur brine production sodium chloride may be implemented.
In the environment of high chlorine, high temperature evaporation obtains crystalline magnesium sulfate monohydrate
Magnesium raw material liquid is mentioned, temperature is greater than 50-80 DEG C, and composition meets Cl-:SO42- molar ratio less than 6, and Mg2+: Na+ rubs
Your concentration ratio is greater than 2, and Mg2+: Na+ molar concentration rate is greater than 2.Terminal point control condition: according to evaporating pressure and boiling temperature come
It determines, Con trolling index can be upgraded to boiling point, and boiling point rises 13 DEG C to 18 DEG C of optimum range.
Case five (proposes magnesium evaporation): 2000 grams of salt-making mother liquors, 60 DEG C, group becomes Na+:1.78%, Mg2+:7.75%,
Cl-:16.18%, SO42-:12.44%, H2O:61.85%；Wherein Cl-:SO42- molar ratio is 3.15,；Mg2+: Na+ mole
Than being 4.1, satisfaction proposes magnesium requirement.Atmospheric evaporation, boiling point reach 115.4 DEG C, stop evaporation, and isothermal is separated by solid-liquid separation.Mother liquid concentration
Na+:2.22%, Mg2+:6.89%, Cl-:20.51%, SO42-:4.11%, H2O:66.27%, wherein Cl-:SO42- moles
It is 2.92 than for 13.49SO42-: Na+ molar ratio 0.44, being greater than 0.25, Mg2+: Na+ molar ratio, is greater than 2.Mass balance steams
Hair amount is 195g, and magnesium sulfate monohydrate amount of precipitation is 230 grams, and eduction rate 74.04%, non-sodium chloride is precipitated.
Case six (proposes magnesium evaporation): 1000 grams of salt-making mother liquors, 61 DEG C, group becomes Na+:1.28%, Mg2+:7.98%,
Cl-:15.79%, SO42-:12.83%, H2O:62.12%；Wherein Cl-:SO42- molar ratio is 3.33, SO42-: Na+ mole
Than being 2.39；Mg2+: Na+ molar ratio is 5.88, and satisfaction proposes magnesium requirement.Atmospheric evaporation, boiling point reach 116.8 DEG C, stop evaporation,
It is filtered using G3 sand core.Isothermal is separated by solid-liquid separation, and filtering is rapid.Mother liquid concentration Na+:1.39%, Mg2+:6.78%, Cl-:
19.32%, SO42-:3.52%, H2O:68.99%, wherein Cl-:SO42- molar ratio is 14.84, SO42-: Na+ molar ratio
0.60, being greater than 0.25, Mg2+: Na+ molar ratio is 4.60, is greater than 2.Evaporation capacity is 47g, and magnesium sulfate monohydrate amount of precipitation is 166.2
Gram, purity 86.7% contains sodium chloride 2.6%, mother liquor entrainment 10.7%.
The mother liquor of magnesium sulfate monohydrate entrainment adopts the method that solvent is replaced or alcohol is washed and reaches dechlorination effect
Case seven (magnesium sulfate monohydrate high-temperature wash): high-temperature wash experiment, magnesium sulfate 70 DEG C or less will as six water or
Epsom salt keeps the form of magnesium sulfate monohydrate, it is necessary to wash at high temperature.150 grams of six magnesium sulfate monohydrate of case is taken, is added
It into 500 grams of 75 DEG C of saturated solution of magnesium sulfate, stirs 10 minutes, mixed liquor atherosclerotic, is filtered using G3 sand core, filtering velocity is crossed in failure
It spends extremely slow.Can not separate under high temperature is unsuccessful in laboratory conditions.
Case eight (washing of magnesium sulfate monohydrate room temperature): room temperature washing experiment, high-temperature material is placed into room temperature and is easy agglomeration, female
Liquid carries the mixture to form a variety of crystallizations water secretly.It is washed using room temperature, since material is reunited, washing is difficult, and washing effect is not achieved
Fruit, and magnesium sulfate monohydrate cannot obtain desired product by the seven every packages of water sulfuric acid.
Case nine (continuous feed continuous evaporative crystallization, mother solution displacement produce low chlorine magnesium sulfate monohydrate): crystallizer adds bottom material
Magnesium brine 1.5L is mentioned, pressure control is constant in 1013mba, and it is constant at 145 DEG C to heat oil temperature.Feed liquid boiling temperature is raised to 114.8
DEG C when, charging is continued between starting, so that feed liquid temperature is not higher than 115 DEG C by charging.Supplement charging adds up to 1.5L.Evaporation adds
Material continues 3 hours, and process discharge 2 times.Slurry is discharged, is filtered with G3 sand core, it is very well.Wet solid phase filter cake is respectively adopted 50 grams
Methanol, ethyl alcohol carry out mother solution displacement 2 times.Through natural air drying, 284 and 345 grams of white crystals products are obtained.It is detected through XRD, is one
Water magnesium sulfate；Grain size analysis average particle size is 168 and 178 microns；It is observed through Electronic Speculum, crystal is spherical druse.Product flowing
Property it is good, whiteness be 91 and 92.Chemical analysis detects magnesium sulfate monohydrate purity and is greater than 95%, and the content of chlorine is respectively 0.75% He
0.95%.
High-sulfur brine with high salt elder generation vacuum salt produces the scheme mistake of magnesium sulfate monohydrate, such as Fig. 1 by salt-making mother liquor again
Shown, material liquid a reaches the condition of restriction after adjusting and converting, and respectively enters salt manufacturing Multi-effect evaporation crystallizer A (1~n-1), and multiple-effect is steamed
Hair is proposed with 3 to 4 effects；Salt manufacturing salt slurry c is separated by solid-liquid separation, is washed and is dried to obtain sodium chloride product.Salt-making mother liquor presses fair current side
Formula goes to 2 effects from 1 effect, until N is imitated；N effect, the discharge amount of mother liquor d is determined according to pressure and feed liquid boiling point.It is qualified
Mother liquor d conduct proposes magnesium solution entrance and mentions magnesium crystallizing evaporator B1；According to pressure and boiling temperature, the discharge for mentioning mother liquid of magnesium e is determined
Amount；Mother liquid of magnesium is mentioned back to salt manufacturing multiple-effect evaporation stages.Magnesium slurry f is mentioned, by separation of solid and liquid B2, mother solution displacement B3, dry B4,
Obtain sulfuric acid monohydrate magnesium products.The alcoholic liquor that mother solution displacement and drying section generate is gentle to pass through solvent recovery B5 recycling design.
Fig. 2,3 explanations: using the high-chlorine high-heat evaporation conditions of this patent, crystalloid magnesium sulfate monohydrate, laboratory dress are obtained
It sets and obtains average particle size greater than 160 microns, commercial plant is expected to obtain bigger granularity, is easy to separation of solid and liquid and purifying products, warp
Mother solution displacement and dry magnesium sulfate monohydrate have good mobility.
Claims (3)
1. a kind of production method for improveing magnesium sulfate monohydrate, it is characterised in that: obtained at 50 DEG C -80 DEG C and mention magnesium raw material containing chlorine is highly concentrated
Liquid, Cl-:SO42- molar ratio should be met less than 6 by mentioning magnesium raw material liquid, and Mg2+: Na+ molar concentration rate is greater than 2.1；Magnesium original will be proposed
Feed liquid imports in container for evaporation, mixes with the mother liquor in container, and Cl-:SO42- molar ratio is greater than 6.5, SO42-: Na+ in mother liquor
Molar ratio is greater than 0.25, and Mg2+: Na+ molar concentration rate is greater than 2.1, in homadamon border, carries out 80 DEG C or more of high temperature and steams
Hair, evaporation terminal are determined according to evaporating pressure and boiling temperature, are upgraded to Con trolling index with boiling point, boiling point rises range 13 DEG C~18
DEG C, complete evaporation of liquid is separated by solid-liquid separation in 70 DEG C or more completions, is obtained magnesium sulfate monohydrate and is crystallized wet solid phase, using mother solution displacement or alcohol
The mode washed cleans magnesium sulfate monohydrate and crystallizes wet solid phase, goes dechlorination component, obtains sulfuric acid monohydrate magnesium crystal.
2. the production method of improvement magnesium sulfate monohydrate according to claim 1, it is characterised in that: using directly preparation or steam
The means for sending out desalination obtain at 50 DEG C -80 DEG C and mention magnesium raw material liquid containing chlorine is highly concentrated.
3. the production method of improvement magnesium sulfate monohydrate according to claim 2, it is characterised in that: the evaporation desalination mistake
Journey is divided into following three kinds of situations:
A. it is less than 0.8 that high-sulfur brine composition, which meets SO42-: Mg2+ molar ratio, and SO42-: Cl- molar ratio is less than 0.25,
Salt manufacturing is directly evaporated, generation mentions magnesium raw material liquid；
B. the molar ratio that high-sulfur brine composition meets SO42-: Mg2+ is greater than 0.8, but when less than 1, then needs to have separated a water sulphur
The mother liquor obtained after the sour wet solid phase of magnesium does circulation fluid, re-evaporation salt manufacturing, and generation mentions magnesium raw material liquid；
C. when the molar ratio that high-sulfur brine composition meets SO42-: Mg2+ is greater than 1, removes part of sulfuric acid sodium or be added containing high concentration
The brine of magnesium chloride makes raw material composition meet (a) or requirement (b)；
It evaporates salt manufacturing and uses negative pressure single-action or the continuous forced evaporation crystallization process of multiple-effect, multiple-effect evaporation salt manufacturing is that material liquid exists
Higher boiling crystallizing evaporator enters system, and salt-making mother liquor uses smooth discharge, in the crystallizing evaporator discharge that boiling temperature is minimum
System, the boiling point of row's salt-making mother liquor evaporator are 50 DEG C~80 DEG C, and salt-making mother liquor respectively imitates discharge for producing magnesium sulfate monohydrate
Solidliquid mixture, by being separated by solid-liquid separation, saturated sodium-chloride salt water washing, being dried to obtain sodium chloride product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713195A (en) * | 2019-11-27 | 2020-01-21 | 青海民族大学 | Method for improving production efficiency of chloride type salt pan and chloride type salt pan product |
| CN111762803A (en) * | 2020-06-17 | 2020-10-13 | 天津长芦汉沽盐场有限责任公司 | Method for producing magnesium sulfate fertilizer by using high-temperature salt |
-
2018
- 2018-09-06 CN CN201811036568.3A patent/CN109179460A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713195A (en) * | 2019-11-27 | 2020-01-21 | 青海民族大学 | Method for improving production efficiency of chloride type salt pan and chloride type salt pan product |
| CN111762803A (en) * | 2020-06-17 | 2020-10-13 | 天津长芦汉沽盐场有限责任公司 | Method for producing magnesium sulfate fertilizer by using high-temperature salt |
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